MODIFICATION OF STARCH PROPERTIES BY REACTIVE EXTRUSION ... · PDF filePROPERTIES BY REACTIVE...
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Edouard Baille-Barrelle (1) • Jean-Christophe Henrion (1) • Xavier Schultze (2) • Julien Portal (2) • Charles Gomes (2) • Gauthier Jarrousse (2) • Caroline Joly (2) • Mireille Arnaud-Roux (2) • Véronique Valero (2) • Claudine Moire (2) • Fabienne Royou-Boutin (2) (1) L'Oreal Research & Innovation, Le Thillay, France. (2) L'Oreal Research & Innovation, Aulnay-sous-Bois, France. Based upon a green process, starch-based extrudates were obtained by reactive extrusion thanks to an experimental design. Samples were characterized in term of processability, solubility and viscosity in water. Only prototypes exhibiting the higher solubility and lower viscosity in water were selected for solubilty in ethanol, GPC and 3 points bending characterizations. Results show that modified starches properties in water are improved in term of solubility (up to 15wt%) and viscosity (until 112cP) versus the native starch (no soluble). With a high amount of ethanol, starch-materials precipitate. The signal of the polymer in GPC is too low which means that the MW of the obtained polymers are under 20 000g/mol. Finally, 3 points bending show that starch-materials have interesting hair fixation properties. CONCLUSION [1] E. Schwach (2004) – Thèse - Etude de systèmes multiphases biodegradables à base d’amidon de blé plastifié, Relations structure – Propriétés, Approche de la compatibilisation [2] G. Moad, Chemical modification of starch by reactive extrusion, Progress in Polymer Science 36 (2011) 218–237 [3] Bettina Wolf, Polysaccharide functionality through extrusion processing, Current Opinion in Colloid & Interface Science 15 (2010) 50–54 REFERENCES Starting Materials: Starch from potatoe (KMC), HydroxyPropylCellulose (Ashland) and Tartaric Acid L(+) (Fluka) Extrusion process: Twin-screw extruder ThermoFisher Eurolab 40D 16mm Experimental design: based on krigeage method Analytical & characterization equipments : - Mettler toledo thermobalance model HB43 Halogen - Rheomat RM200 Lamy / MS-R3 - Gel Permeation Chromatography aqueous : Waters equipment with Shodex column / detector RI - Bending tests MATERIAL AND METHODS Native and modified starch molecular weight are not quantifiable in these conditions Molecular Weight of modified starch are lower than HydroxyPropylCellulose SOLUBILITY AND VISCOSITY TESTS : Evaluation of solubility and viscosity in 3 different solutions Modified Starches are dispersible with a low viscosity in the water. Modified Starches precipitate with increasing amounts of Ethanol Color of the solution can be induced by process parameters : ✓ High temperature ✓ High Screw rotation speed ✓ Low feeding rate GEL PERMEATION CHROMATOGRAPHY RESULTS : HIGHTHROUGHPUT EXPERIMENTATION : 3 POINTS BENDING EVALUATION EXPERIMENTAL DESIGN : 70 TRIALS PERFORMED Screening of process and compositions parameters X1 : Temperature (T°C) = [170 to 200] X2 : Screw rotation speed (RPM) = [200 to 1000] X3 : Feeding rate (g/h) = [500 to 1500] X4 : Starch (wt%) [50 to 90] X5 : HPC (wt%) [10 to 40] X6 : Tartaric acid (wt%) [5 to 20] Figures in orange are parameters and compositions showing the bests results Evaluations Processability (Y1) Solubility (Y2) Viscosity (Y3) RESULTS The aim of this work is to change starch physico-chemical properties. The approach consists in associating starch with a polymer to keep on one hand a desired rigidity and on the other hand an acceptable solubility. Such association, excluding a mere physical blending, implies chemical bonds being created to avoid phase separation. Hydroxypropylcellulose was chosen as solubilizing agent and acid tartaric as esterification agent to bind the two polysaccharides. This esterification reaction was performed by an eco-friendly extrusion process. This one-step continuous process allows high viscosity component to be used without adding solvent, lowers the amount of waste and optimizes energy savings and mass transfers. The immense combination of processing parameters and compositions led to a high number of possible trials, thus imposing the creation of an internal experimental design. INTRODUCTION Starch is known for its high intrinsic rigidity, excellent safety profile, and green value as renewable. Unfortunately, its physicochemical properties impair its formulation in cosmetic formulations which require solubility and low viscosity in Water/Ethanol solution. A study was led by L’Oréal Advanced Research in order to valorize this polysaccharide for cosmetic applications, especially as an ingredient in hair setting products, considering that the high intrinsic rigidity of such polymer could logically offer a high holding effect. The development of potato starch-based material was performed by extrusion using HydroxyPropylCellulose as solubility agent and Tartaric Acid as linker. From an experimental design, best propotypes showed an improvement of starch-based material solubility up to 15wt% in water with a low viscosity; contrary to native starch which is low soluble and develops high viscosity in water. Furthermore, these new materials obtained by a green process showed interesting hair setting properties. ABSTRACT MODIFICATION OF STARCH PROPERTIES BY REACTIVE EXTRUSION FOR COSMETIC APPLICATIONS Results of sample PEX 8-2 * Viscosity not measured because sample is precipitating Native and modified starch molecular weight are not quantifiable in these conditions
Transcript of MODIFICATION OF STARCH PROPERTIES BY REACTIVE EXTRUSION ... · PDF filePROPERTIES BY REACTIVE...
Edouard Baille-Barrelle(1) • Jean-Christophe Henrion(1) • Xavier Schultze(2) • Julien Portal(2)
• Charles Gomes(2) • Gauthier Jarrousse(2) • Caroline Joly(2) • Mireille Arnaud-Roux(2) •
Véronique Valero(2) • Claudine Moire(2) •Fabienne Royou-Boutin(2)
(1) L'Oreal Research & Innovation, Le Thillay, France. (2) L'Oreal Research & Innovation, Aulnay-sous-Bois, France.
Based upon a green process, starch-based extrudates were obtained by reactive extrusion thanks to an experimental design. Samples were characterized in term of processability, solubility and viscosity in water. Only prototypes exhibiting the higher solubility and lower viscosity in water were selected for solubilty in ethanol, GPC and 3 points bending characterizations. Results show that modified starches properties in water are improved in term of solubility (up to 15wt%) and viscosity (until 112cP) versus the native starch (no soluble). With a high amount of ethanol, starch-materials precipitate. The signal of the polymer in GPC is too low which means that the MW of the obtained polymers are under 20 000g/mol. Finally, 3 points bending show that starch-materials have interesting hair fixation properties.
CONCLUSION
[1] E. Schwach (2004) – Thèse - Etude de systèmes multiphases biodegradables à base d’amidon de blé plastifié, Relations structure – Propriétés, Approche de la compatibilisation[2] G. Moad, Chemical modification of starch by reactive extrusion, Progress in Polymer Science 36 (2011) 218–237[3] Bettina Wolf, Polysaccharide functionality through extrusion processing, Current Opinion in Colloid & Interface Science 15 (2010) 50–54
REFERENCES
Starting Materials:Starch from potatoe (KMC), HydroxyPropylCellulose (Ashland) and Tartaric Acid L(+) (Fluka)
Extrusion process: Twin-screw extruder ThermoFisher Eurolab 40D 16mm
Experimental design: based on krigeage method
Analytical & characterization equipments :- Mettler toledo thermobalance model HB43 Halogen- Rheomat RM200 Lamy / MS-R3- Gel Permeation Chromatography aqueous : Waters equipment with Shodex column / detector RI- Bending tests
MATERIAL AND METHODS
Native and modified starch molecular weight are not quantifiable in these conditions Molecular Weight of modified starch are lower than HydroxyPropylCellulose
SOLUBILITY AND VISCOSITY TESTS :
Evaluation of solubility and viscosity in 3 different solutions
Modified Starches are dispersible with a low viscosity in the water.
Modified Starches precipitate with increasing amounts of Ethanol
Color of the solution can be induced by process parameters : ✓ High temperature ✓ High Screw rotation speed ✓ Low feeding rate
GEL PERMEATION CHROMATOGRAPHY RESULTS : HIGHTHROUGHPUT EXPERIMENTATION : 3 POINTS BENDING EVALUATION
EXPERIMENTAL DESIGN : 70 TRIALS PERFORMED
Screening of process and compositions parameters
X1 : Temperature (T°C) = [170 to 200]X2 : Screw rotation speed (RPM) = [200 to 1000]X3 : Feeding rate (g/h) = [500 to 1500]X4 : Starch (wt%) [50 to 90]X5 : HPC (wt%) [10 to 40]X6 : Tartaric acid (wt%) [5 to 20]
Figures in orange are parameters and compositions showing the bests results
Evaluations
Processability (Y1)Solubility (Y2)Viscosity (Y3)
RESULTS
The aim of this work is to change starch physico-chemical properties. The approach consists in associating starch with a polymer to keep on one hand a desired rigidity and on the other hand an acceptable solubility. Such association, excluding a mere physical blending, implies chemical bonds being created to avoid phase separation. Hydroxypropylcellulose was chosen as solubilizing agent and acid tartaric as esterification agent to bind the two polysaccharides.
This esterification reaction was performed by an eco-friendly extrusion process. This one-step continuous process allows high viscosity component to be used without adding solvent, lowers the amount of waste and optimizes energy savings and mass transfers. The immense combination of processing parameters and compositions led to a high number of possible trials, thus imposing the creation of an internal experimental design.
INTRODUCTION
Starch is known for its high intrinsic rigidity, excellent safety profile, and green value as renewable. Unfortunately, its physicochemical properties impair its formulation in cosmetic formulations which require solubility and low viscosity in Water/Ethanol solution. A study was led by L’Oréal Advanced Research in order to valorize this polysaccharide for cosmetic applications, especially as an ingredient in hair setting products, considering that the high intrinsic rigidity of such polymer could logically offer a high holding effect. The development of potato starch-based material was performed by extrusion using HydroxyPropylCellulose as solubility agent and Tartaric Acid as linker.From an experimental design, best propotypes showed an improvement of starch-based material solubility up to 15wt% in water with a low viscosity; contrary to native starch which is low soluble and develops high viscosity in water. Furthermore, these new materials obtained by a green process showed interesting hair setting properties.
ABSTRACT
MODIFICATION OF STARCH PROPERTIES BY REACTIVE EXTRUSION FOR COSMETIC APPLICATIONS
Results of sample PEX 8-2* Viscosity not measured because sample is precipitating
Native and modified starch molecular weightare not quantifiable in these conditions
